Note: Descriptions are shown in the official language in which they were submitted.
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Description
TAR-DEPLETED LIQUID SMOKE AND METHOD OF MANUFACTURE
Technical Field
The present invention relates, in general, to a
liquid smoke composition. Such liquid smoke compositions
are used to color and flavor edible foodstuffs. More
particularly, the present invention relates to a liquid
smoke composition which has been refined to remove
selected tar components therefrom.
Background of the Invention
Foods have been smoked since humans first used fire
to prepare meals. Smoking of foods has provided flavor,
color, and preservation. Initially, preservation was the
most critical reason to smoke foods; but as technology
advanced, flavor and color have become the main reasons to
smoke foods.. As societies became more industrialized, the
shift from home or individual smoking to processing in
specialized plants led the need for better control of
smoking procedures. Moreover, increased productivity
drove the desire for more consistent smoke application
techniques.
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As a result, liquid smoke compositions (also known as
liquid smoke solutions, and colloquially referred to as
liquid smokes) were developed as a replacement for smoking
of food by direct contact with smoke, and such
compositions have become a standard industry practice.
When applied to the surface of meats and other
proteinaceous foodstuffs,. such as various types of
sausages, frankfurters, bolognas, beef rolls, hams, and
the like, liquid smoke gives the item a characteristic
smoke flavor and produces a dark smoked color. The
achievement of a smokehouse-like product by application of
an aqueous smoke solution to a foodstuff requires the
control and balancing of many variables such as the food
composition, temperature, humidity, processing time,
contact time, amount of liquid smoke, and concentration of
liquid smoke.
It is well known to those skilled in the art that
liquid smoke compositions contain a wide array of chemical
compounds, and over 400 such compounds have been
identified. Nevertheless, it is also well known to those
skilled in the art that liquid smoke compositions are
characterized by their content of certain classes of
compounds, namely, acids (% titratable acidity), phenols,
and carbonyls.
The acids are preservatives, and, of course, pH
control agents, as a result of which commercial liquid
smoke compositions typically have a pH under about 2.5,
and more typically under about 2.3, and a % titratable
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acidity by volume from about 3% to about 18%. The phenols
give flavor, and also aroma, to liquid smoke compositions,
and commercial compositions typically have a phenols
content from about 3 to about 45, and more typically, from
about 14 to about 30 mg/ml. The carbonyls impart the
brown color to liquid smoke compositions. The phenols and
the carbonyls can be measured as described in the below-
mentioned U.S. Patent No. 4,431,032 to Nicholson. The
color-forming potential of liquid smoke compositions can
be measured by the well-known Browning Index procedure
described in the below-mentioned U.S. Patent No. 4,994,297
to Underwood or by the well-known Staining index procedure
involving reaction of liquid smoke with glycine, as
described below. It is noted that the acids and carbonyls
are secondary in- contributing to the flavor of liquid
smoke compositions.
More specifically, liquid smoke was developed over 65
years ago, and is the aqueous condensate of natural wood
smoke, as described in U.S. Patent No. 1,753,358 issued in
1930 to Wright. Also, of interest in connection with
older manufacturing procedures for liquid smoke is U.S.
Patent No. 2,400,466 issued in 1946 to Reiter et al.
Improved liquid smoke compositions and techniques for
manufacture thereof are described in U.S. Patent No.
3,106,473 to Hollenbeck, U.S. Patent No. 3,873,741 to
Melcer et al., U.S. Patent No. 4,298,435 to Ledford, U.S.
Patent No. 4,154,866 to Dainius et al., and U.S. Patent
No. 4,994,297 to Underwood.
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While the advent of liquid smoke compositions has
significantly improved meat processing, attempts have been
made over the last 20 years or so to deal with the tar
problem of liquid smoke. Upon storage of a liquid smoke
product, the tar will settle forming a water insoluble,
sticky, viscous precipitate on the bottom of the container
for the liquid smoke.
Furthermore, although water is present in liquid
smoke, it is not totally water soluble, which exacerbates
the tar problem. More specifically, for commercial
application of liquid smoke to a foodstuff, liquid smoke
is typically diluted with water in an amount that results
in 2 to 5 times the original volume of liquid smoke.
However, the tar precipitate will also occur upon dilution
of liquid smoke with water, and thus can easily be drawn
into the piping of a system used in applying the liquid
smoke to the foodstuff.
In connection therewith, it is noted that a liquid
smoke composition and related process for maintaining the
tar component of the liquid smoke in suspension so that
the tar does not form undesirable solids during storage is
described, in U.S. Patent No. 4,112,133 to Rao. More
particularly, the patent to Rao is directed to admixing
liquid smoke with a fatty compound, such as a poly-
oxyethylene sorbitan monooleate, a polyoxyethylene
sorbitan monostearate, or a polyoxyethylene sorbitan
monopalmitate to emulsify the tar.
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Removing the tar instead of keeping it in emulsion is
achieved by a solvent extraction process used on liquid
smoke to create a desirable tar-depleted liquid smoke
supernatant fraction and an undesirable tar-containing
fraction, followed by gravity separation of the two
fractions, as is described in U.S. Patent Nos. 4,431,032,
4,431,033, and 4,496,595,= all to Nicholson and in U.S.
Patent No. 4,592,918 to Chiu. Solvents such as
dichloromethane or chloroform are used. Related thereto
is the tar removal process described in U.S. Patent No.
4,504,507 to Nicholson, wherein the pH of liquid smoke is
raised above 4 to create a desirable tar-depleted liquid
smoke supernatant fraction and an undesirable tar-
containing fraction, followed by gravity separation of the
two fractions.
The four patents to Nicholson also describe treating
a surface of a food casing, such as a fibrous, cellulosic
food casing used for sausages, with the tar-depleted
liquid smoke. Furthermore, U.S. Patent No. 5,288,532 to
Juhl et al. describes a polymeric plastic film food
casing, such as one made of a blend of ethylene vinyl
acetate copolymer and polyethylene oxide, which during
extrusion of the plastic film, has liquid smoke blended
with the polymer beads. The liquid smoke then transfers,
or bleeds out from the film, to the foodstuff packaged
with the film.
Lastly, of interest in relation to removal of
undesired components, from liquid smoke is the process
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described in U.S. Patent No. 4,959,232 to Underwood, which
is directed to passing liquid smoke through a column of
both ionic and non-ionic polymeric resin beads (suitable
resins are copolymers of alkylacrylates and cross-linking
polyvinylidene), or alternatively mixing the liquid smoke
with the resin beads in a batch process, to remove flavor
components thereof so that more of the resultant liquid
smoke can be employed to impart more of the brown coloring
to the treated foodstuff.
The disclosures of all of the above-mentioned patents
may be referred to for further details.
Despite the above-discussed procedures to deal with
removing or keeping suspended certain components of liquid
smoke (such as removing tar by solvent extraction of
liquid smoke or keeping tar in suspension by adding a
sorbitan fatty compound to liquid smoke), nevertheless,
problems still exist with such procedures. For instance,
the solvent extraction process of the patents to Nicholson
and the resin treatment process of the patent to Underwood
both have a shortfall in that these processes leave
residual solvents that are directly added by Nicholson or
used by Underwood to condition the resin.
Keeping the tar suspended in accordance with the
process of the patent to Rao requires addition of sorbitan
fatty compounds which dilutes the liquid smoke, resulting
not only in increased usage requirements but also impeding
the color-forming reaction whereby the smoke can be rinsed
away from the foodstuff if not properly set during
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application to the foodstuff. With this process, the tar
is still in the liquid smoke so that the tar, as well as
the added sorbitan fatty compound, is being eaten by the
consumer of the smoke-treated foodstuff. Moreover,
sorbitan fatty compounds have not been approved for
application to foodstuffs in some countries, which limits
the distribution of these smoke-treated foodstuffs.
Thus, it is desirable to find an improved liquid
smoke composition that is tar-depleted and a method for
the manufacture thereof, which composition and method
obviate the above-mentioned problems.
Summary and Objects of the Invention
Accordingly, the present invention provides a method
for making a tar-depleted liquid smoke composition
comprising the step of contacting a starting-material
liquid smoke composition having a phenols content, the
phenols content .including a tar component, with an
activated carbon having sufficient active sites to produce
a tar-depleted liquid smoke composition having a phenols
content with a reduced tar component such that the tar-
depleted liquid smoke is totally water miscible.
Additionally, the present invention provides for a
tar-depleted liquid smoke composition comprising a totally
water-miscible tar-depleted liquid smoke composition, the
tar-depleted liquid smoke composition being derived from
a starting-material liquid smoke composition containing
phenols, the phenols including a tar component, wherein
the phenols of the tar-depleted liquid smoke composition
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has a reduced tar component from contacting thestarting-
material liquid smoke composition with an activated carbon
having sufficient sites to produce the reduction.
Preferably, the starting material liquid smoke
composition has a phenols content of about 3 to about 45,
and more preferably, about 14 to about 30 mg/ml.
Typically, the phenols content of the resultant tar-
depleted liquid smoke composition will be reduced by about
10% by weight to about 90% by weight, as compared to the
phenols content of the liquid smoke composition starting
material.
However, in an alternative embodiment, the tar-
depleted liquid smoke may be concentrated, such as by
t_
vacuum evaporation, and the concentrate will have a
phenols content higher than that of the liquid smoke
composition starting material but still will be totally
water miscible.
The present invention also contemplates a food casing
treated with the tar-depleted liquid smoke composition.
The treatment may be by spraying the tar-depleted liquid
smoke onto a surface of the casing, or in the event that
the casing-is of extruded polymeric plastic film, the tar-
depleted liquid smoke may be sprayed onto a surface of the
film or may be incorporated into the extruder with the
polymeric resin beads and thus blended into the resultant
plastic film.
The present invention also contemplates a
proteinaceous foodstuff, such as various types of
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sausages, frankfurters, bolognas, beef rolls, hams, and
the like, treated with the novel tar-depleted liquid smoke
composition.
Accordingly, it is an aspect, of the present invention
to provide a liquid smoke composition and related method
of manufacture, wherein the composition is tar-depleted
and therefore will not form tar precipitate upon dilution
with water.
Hence, it is an advantage of the present invention
that the liquid smoke composition is totally water
miscible since when liquid smoke is applied to foodstuffs
or food casings it is typically diluted with water and
forms tar precipitates that gum the piping system of the
application apparatus, which gumming will not occur with
the tar-depleted liquid smoke composition of the present
invention.
Some of the aspects and advantages of the invention
having been stated above, other aspects, as well as other
advantages, will become evident as the description
proceeds, when taken in conjunction with the Laboratory
Examples and detailed description hereinbelow.
Detailed Description of the Invention
The present invention is directed to a tar-depleted
liquid smoke composition manufactured by contacting liquid
smoke with activated carbon having sufficient active sites
to reduce the tar component of liquid smoke. While it is
not intended to be bound to any theory, it is believed
that the tar component is part of the phenols component of
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liquid smoke, as further explained below- The tar-
depleted liquid smoke composition of the invention still
retains smoke coloring and smoke flavoring capability.
As can be seen from the Laboratory Examples below,
the inventive method resulted. in a reduction of the
phenols in the resultant liquid smoke as compared to the
starting material liquid smoke. When the resultant was
then diluted with water, no tar precipitated. Rather, the
diluted liquid smoke remained clear from a dilution with
water of up to 5 times the original volume of the
resultant, and thus the resultant was totally miscible
with water.
In an alternative embodiment, when the resultant was
concentrated by vacuum evaporation to remove some of the
water thereof, the concentrate had a phenols content
higher than that of the starting material liquid smoke.
However, the concentrate, upon dilution with water of up
to 5 times, still remained clear. (See sample no. 4 of
Example 4 below.)
Moreover, with certain activated carbons that have
insufficient active sites, although the phenols content
was lower in the resultant than in the starting material
liquid smoke, the resultant still was tar-containing.
(See Example 5 below.) Thus, for those activated carbons
with sufficient active sites, it appears that the
inventive method reduces the phenols by reducing the tar
component thereof.
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In selected Laboratory Examples below, in; order to
produce a tar-depleted liquid smoke, a tar-containing
liquid smoke thus treated by the method of the present
invention was Code 10, which is commercially available
from Hickory Specialties, Inc., of Brentwood, Tennessee.
In one of the Laboratory Examples below, the liquid smoke
starting material employed was SUPERSMOKE, also
commercially available from Hickory Specialties, Inc., and
manufactured by a well known vacuum evaporation process
that concentrates Code 10 by removing some of the water
thereof. As a result, SUPERSMOKE has a typical acidity of
about 16%, whereas Code 10 has a typical acidity of about
11%. Other commercially available liquid smoke
compositions also may be employed with the method of the
present invention to produce a tar-depleted liquid smoke.
Each of the activated carbon products useful in the
present invention for treating the liquid smoke starting
material, such as Code 10, has sufficient active sites in
the carbon particles to produce a tar-depleted liquid
smoke composition-having a phenols content with a reduced
tar component such that the tar-depleted liquid smoke is
totally water miscible. As compared to the liquid smoke
starting material, the tar-depleted liquid smoke typically
has a phenols content reduced by at least about 10% by
weight, and the reduction may be up to about 90% by
weight, but more typically is up to about 85% by weight.
Preferably, the reduction is at least about 15% by weight,
and more preferably at least about 30% by weight. In
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connection therewith, it is reiterated that the tar-
depleted liquid smoke may be concentrated by the vacuum
evaporation process (the process noted above for making
SUPERSMOKE from Code 10 and well known to those skilled in
the art), and hence, the concentrate will be tar-depleted
but have a phenols content higher than that of the liquid
smoke starting material.
The activated carbon products having sufficient
active sites and employed in the present invention were
purchased from Calgon carbon corporation of Pittsburgh,
Pennsylvania, and are described in their sales brochure
entitled "Activated Carbon Products for Liquid and Vapor
Phase Applications" (November, 1993). The preferred
activated carbon having sufficient active sites for use in
the present invention is sold by Calgon under the trade
name ADP, and is pulverized with a U.S. standard sieve
size of 80 x 325. Less preferred is the activated carbon
having sufficient active sites and sold by Calgon under
the trade name APA, which is granular and has a U.S.
standard sieve size of 12 x 40. Also useful, but much
less preferred because either much more must be used or
the contact time with the commercially available liquid
smoke must be much longer, is an activated carbon having
sufficient active sites and sold by Calgon under the trade
name PWA, which is pulverized. Calgon does not indicate
in their sales brochure what is the U.S. standard sieve
size of PWA, but has made publicly known that PWA is not
as highly activated as either APA or ADP.
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Any carbon having sufficient active sites or mixtures
of such carbons may be employed in the present invention.
Therefore, an activated carbon having sufficient active
sites may be selected from the group consisting of ADP,
APA, PWA, and combinations thereof. In connection
therewith, it is noted that certain activated carbons do
not have sufficient active' sites and do not work in the
present invention. One such activated carbon with
insufficient active sites is sold under the trade name TOG
by Calgon, and is further described in Example 5 below.
As described in their technical information brochure
entitled "Activated Carbon Principles" (May, 1993), Calgon
manufactures activated carbon by treating such materials
as coal, wood, peat, coconut shells, and petroleum coke
with a heat and steam process, resulting in graphite
platelets. As explained in their brochure, part of the
material is selectively oxidized with an acid gas mixture
of water vapor and carbon dioxide to develop a certain
pore structure, i.e.,. create active sites. More
particularly, the amount of activation is related to the
resultant pore volume of the activated carbon, which
affects the Van der Waals force that fixes the products to
be adsorbed to the activated carbon.
With the present invention, the contact of the liquid
smoke with the activated carbon in order to produce tar-
depleted liquid smoke should be under ambient conditions
of temperature and pressure. Furthermore, the time of
contact should be about at least 15 minutes, and may be up
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to about 12 hours or more, depending on thecparticular
type, amount, and pore volume. of the activated carbon
employed. More preferably, the contact time should be
about 0.5 hours to about 9 hours, and most preferably
about 1.5 hours to about 5 hours.
Batch processes, wherein the activated carbon
particles are placed in liquid smoke in a container with
stirring, followed by filtration to separate the particles
from the resultant tar-depleted liquid smoke, may be
employed. Besides filtration, the method to separate the
particles may include gravity decanting, liquid cycloning,
and centrifugal decanting. However, in a commercial
setting in a factory, a column process should be more
economically viable. In a column process, a cylindrical
container is packed with a bed of the activated carbon
particles, and then the liquid smoke is passed downf low
through the column, and effluent of tar-depleted liquid
smoke is collected as it exits the bottom of the column.
The activated carbon particles useful in the present
invention adsorb phenols (including the tar-producing
components thereof) from the starting-material liquid
smoke, and the bound phenols can be displaced from the
spent activated carbon particles under appropriate
conditions. The removal of adsorbates, such as by
backwash, from spent activated carbon particles is well
known to those skilled in the art, and will allow the
carbon to be reused and recycled.
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As noted above, food casings may be treated with the
tar-depleted liquid smoke composition. In the event that
the casing is the fibrous type, the treatment may be by
spraying the tar-depleted liquid smoke onto a surface of
the casing. Typical fibrous casings are cellulosic in
nature. In the event that the casing is of extruded
polymeric plastic film, the tar-depleted liquid smoke may
be sprayed onto the surface of the film. Alternatively,
the tar-depleted liquid smoke may be incorporated into the
extruder with the polymeric resin beads and thus blended
into the resultant plastic film. Typical polymeric
plastic films include, but are not limited to, films of
polymers selected from the group consisting of ethylene
vinyl acetate, ethylene acrylic acid, ethylene methacrylic
acid, linear low density polyethylene, very low density
linear low density polyethylene (sometimes referred to as
ultra low density polyethylene), and combinations thereof.
Additionally, a proteinaceous foodstuff may be
treated with the tar-depleted liquid smoke composition,
such as by spraying on the surface thereof. Examples of
various types of proteinaceous foodstuffs include, but are
not limited to, sausages, frankfurters, bolognas, beef
rolls, hams, and combinations thereof.
Laboratory Examples
In the Laboratory Examples below, the methods used to
determine the phenols and the carbonyls are well known to
those skilled in the art and are set out at columns 11 and
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12 in the above-mentioned U.S. Patent No. % 431,032 to
Nicholson. Also, in the Laboratory Examples below, the
methods used to determine the staining index and the acid
percent are well=known.to those skilled in the art, and
are set out as follows:
STAINING INDEX
Reagent of 2.5% Glycine in 95% Acetic Acid. Slurry
2.50 gram of glycine (Eastman #445) with 5.0 ml distilled
water in a 150 ml beaker. Add about 70 ml glacial-acetic
and heat on a steam bath, stirring occasionally to
dissolve the glycine. Transfer to a 100 ml volumetric
flask, cool to room temperature, and make to volume with
glacial acetic acid which is used to rinse the original
beaker. Filter the solution prior to use if any glycine
crystallizes out. The solution is stable for at least 3
weeks, and probably indefinitely.
5% Liquid Smoke Solution. Dilute 2.50 ml of liquid
smoke to 50.0 ml with glacial acetic acid.
Reaction:
1. Using two 25 ml graduated test tubes, add
1.0 ml of the 5% liquid smoke solution to
10.0 ml of glycine reagent and add 1.0 ml
of the 5% liquid smoke solution to 10 ml of
glacial acetic acid (blank).
2. Cover each tightly with a square of
parafilm, and mix by swirling and place in
a water bath at 85 C for 30 minutes.
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3. Transfer to a cold water bath and dilute
partially with distilled water to speed
cooling. When at room temperature, finish
diluting to the 25 ml mark and mix by
inversion.
4. Set a spectrophotometer to 0 using
distilled water.- Read the absorbance of
each solution in a 0.5 inch cuvette using
a spectrophotometer at 440 millimicrons.
5. Calculate the net absorbance by subtracting
the reading of the blank (consisting of 1.0
ml of 5% liquid smoke solution, 10.0 ml
glacial acetic acid, and distilled water to
25 ml) from the reading of the test sample.
6. Calculate the staining index: SI = Net
Absorbance x 100.
PERCENTAGE OF ACETIC ACID
Pour 250 ml of distilled water into a clean 400 ml
beaker. Introduce 6 ml of liquid smoke. Standardize pH
meter with pH 7 buffer solution. The pH meter should be
on 7.00. If not, use control knob and place it there.
Rinse off glass electrode with distilled water from spray
bottle. Place beaker of water-smoke mixture on testing
platform, and lower pH electrodes. Stir mixture, adding
in standard 1.0 Normality sodium hydroxide solution. Add
the sodium hydroxide until pH meter reads 7.00. The
amount of milliliters of sodium hydroxide put into the
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water-smoke mixture is the percentage of acetic acid. For
instance, 1 ml of sodium hydroxide entering into the
smoke-water mixture will count 1 point acetic acid until
the pH meter reaches a value of 7.00. In other words, if
9.4 ml of 1.0 N sodium hydroxide solution is introduced,
the acetic acid reading will be 9.4% of acetic acid by
volume.. The calculations are as follows:
% acetic acid = [(ml of NaOH) X (Normality
of NaOH) X (equivalent weight of acetic acid)]
divided by ml of liquid smoke.
% acetic acid = [(11.3 ml of NaOH) X (1.0
Normality) X (approximately 60)] divided by 6.0 ml
of liquid smoke,
and thus,
% acetic acid = 11.3.
Example 1 (column)
A cylindrically shaped, metal, 55 gallon drum of
about 22.5 inches (about 57 cm) in diameter and about 34
3/8 inches (about 87 cm) in height was fitted with a
bottom drain port and a top feed tube. Into the drum was
placed about 160 pounds [about 352 kg, which was a column
height of about 28 inches (about 71 cm)] of APA, a
granular acid-washed activated carbon from Calgon.
Liquid smoke having a titratable acidity of 11.6%
(about 30 gallons of Code 10 from Hickory Specialties,
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Inc.) was fed into the drum and allowed to sit overnight
(about 12 hours), and the resultant tar-depleted effluent
drained from the bottom port of the drum is designated in
Table 1 below as the 1st sample. On the following day, a
continuous gravity feed of Code 10 was initiated via the
top feed tube and drained via the bottom port. Flow rate
through the drum was 30 gallons per hour, which was a
contact time of about 2 hours. The effluent liquid smoke
samples were collected sequentially in 55 gallon drums,
and are designated in Table 1 below as the 2nd, 3rd, 4th,
5th, 6th and 7th samples. The samples were analyzed with
the following results reported in Table 1 below:
TABLE 1
Staining Carbonyls Phenols Water Specific
Sample Acidity (%} pH Index (a/1 00 n) m ml Dilution Gravity
Code
10 feed 11.0 2.11 90.0 22.9 18.7 Cloudy 1.077
1st 8.7 1.97 58.6 11.2 2.7 Clear 1.050
2nd 11.5 2.01 91.8 20.3 6.3 Clear 1.079
3rd 11.2 2.05 98.0 19.6 10.0 Clear 1.080
4th 10.9 2.05 98.1 20.6 16.6 Clear 1.082
5th 10.8 2.05 93.5 20.3 16.3 Clear 1.082
6th 10.8 2.06 87.8 20.3 19.0 Slightly 1.082
Cloudy
7th 10.9 2.06 91.3 20.3 17.1 Cloudy 1.082
For water dilution, water was added to create a 2x
volume for all samples. The Code 10 feed sample exhibited
cloudiness (i.e., tar precipitate) from the dilution,
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which was expected as Code 10 is a commercially available
tar-containing liquid smoke.
For the 2nd through 5th samples, water to a 2x volume
did not result in tar precipitate and thus more water was
added to create a 5x volume. Still the samples remained
clear, which illustrates these tar-depleted samples were
totally water miscible. 'Furthermore, the data clearly
shows a reduction in total phenolic compounds which
parallels the water miscibility, for each of the 1st
through 5th samples. Consequently, a blend of the 1st
through 5th samples should be efficacious as a tar-
depleted liquid smoke having staining properties
essentially the same as the starting material. Also, each
of the 1st through 5th samples could be used individually
for treating a foodstuff, depending on the desired flavor
and browning.
Thereafter, for the 6th and 7th samples, the
activated carbon particles were apparently spent and
should be backwashed to remove adsorbates since the
phenols % was about the same as that of the starting Code
10 feed and only a 2x water dilution resulted in
cloudiness.
Example 2 (batch)
The impact of carbon particle size on the
effectiveness in generating tar-depleted liquid smoke was
evaluated using powdered and granular forms of the same
activated carbon. Carbon APA from Calgon is a granular
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form of highly activated carbon while ADP from3r:.Calgon is
a powdered form of the same material.
To equal aliquots (100 ml) of Code 10 liquid smoke
(10.7% titratable acidity) was added each of the activated
carbons in various amounts. The samples were mixed with
a magnetic stirrer for the time intervals indicated in
Table 2 below, and at those times,-small (1 ml) portions
were taken and filtered through a Whatman #1 filter paper
to remove the carbon.
Each filtered sample of liquid smoke was mixed with
2 to 5 times its volume of water to judge miscibility.
The lack of tar or precipitate formation for 2 hours
(sample remained clear) was established as the endpoint in
determining that the sample was totally water miscible,
and those are reported in Table 2 below.
The following Table 2 shows the similarity in minimum
carbon levels necessary to achieve a tar-depleted liquid
smoke with total water miscibility, and highlights the
increased carbon required to achieve miscibility at
shorter contact times for granular carbon as compared to
powdered carbon. The differential in carbon amounts for
shorter time periods is proportional to the adsorption
rate of tar-forming components to internal active sites in
the carbon matrix.
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TABLE 2
Granular vs. Powder Carbon Comparison
Amount of Carbon Contact Time of Magnetic
Type of Carbon (grams) Stirring (hours)
APA 15 0.75
12.5 1.25
1.7
8 3
5.25 4.25
10 4 8
ADP 8 1.5
5 5.25
4 8.5
As can be seen, the powdered ADP had more active
sites on its surface than the granular APA, since 8 grams
of powdered ADP produced tar-depleted liquid smoke with
1.5 hours of contact time, whereas to produce tar-depleted
liquid smoke in about the same amount of time, 10 grams
(1.25 hours) to 12.5 grams (1.75 hours) of granular APA
were required.
Example 3 (batch)
The impact of the amount of carbon activation on
production of totally water miscible smoke was evaluated
using Calgon powdered carbons ADP and PWA. These two
carbons are derived from the same source materials but
Calgon reports that they differ in amount of activation
with ADP having a higher activation level.
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The procedure of Example 2 was repeated and different
levels of carbon were mixed with 100 ml aliquots of Code
liquid smoke (10.7% titratable acidity). It was found
that the more activated a given carbon, the greater the
5 efficiency of removing tar-forming materials. The results
are reported in the following Table 3 which shows the
significant impact of activation level on carbon
efficiency.
TABLE 3
10 Carbon Powder Comparison
Amount of Carbon Contact Time of Magnetic
Type of Carbon (prams) Stirring (hours)
ADP 8 1.5
5 5.25
4 8.5
PWA 15 0.25
12.5 1.0
8 8.5
As can be seen, 8 grams of the more activated
powdered ADP produced tar-depleted liquid smoke with only
1.5 hours of contact time, whereas the same amount of 8
grams of the less activated powdered PWA took 8.5 hours to
produce tar-depleted liquid smoke.
Example 4 (column)
The following Table 4a depicts the products used to
produce tar-depleted liquid smokes of different
concentrations, employing the column procedure of Example
1 with Calgon activated carbon APA, except that the column
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was continuous by linking 6 drums together. The f low rate
was 2 gallons/minute through a total of about 810 pounds
of carbon for all 6 drums (i.e., 135 pounds/drum). To
determine water miscibility, the effluent was diluted with
water to 5x the previous volume.
TABLE 4a
Commercially Existing Products
(1) Code 10 (basic liquid smoke)
(2) SUPERSMOKE (smoke concentrate)
Products of Invention
(3) Tar-depleted (resultant from carbon treatment
of Code 10)
(4) Tar-depleted concentrate (made from using on
no.3 the same vacuum evaporation process as is used
commercially
to make SUPERSMOKE from Code 10)
(5) Tar-depleted (resultant from Carbon treatment
of SUPERSMOKE)
The composition of each of these products is defined
in the following Table 4b with products identified by the
number in parenthesis.
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TABLE 4b
Product
Test Parameter (1) (2) (3) (4) (5)
Titratabie Acidity (%) 10.9 16.2 11.1 16.95 17.9
Staining Index 102.3 201.8 88.7 217.2 232.6
Specific Gravity 1.080 1.168 1.074 1.172 1.176
Carbonyls (g/100 ml) 22.1 39.5 20.4 36.9 36.3
Phenols (mg/ml) 17.6 28.4 9.1 23.6 16.8
Water Solubility No No Yes Yes Yes
It is readily apparent that various products can be
derived through alternative pathways. Specifically, the
efficacy of activated carbons in producing totally water-
miscible smoke products is not impacted by concentration
of tar-depleted Code 10 (product no. 3) to create tar-
depleted SUPERSMOKE concentrate (product no. 4), as
compared making tar-depleted SUPERSMOKE (product no. 5)
directly by carbon treatment of commercial SUPERSMOKE
(product no. 2). Thus, product no. 4 has a phenols
content greater than that of the starting material, namely
product no. 1, but product no. 4 is still totally, water
miscible, as it is tar-depleted.
Example 5 (comparison)
The impact of an activated carbon with insufficient
active sites to produce a tar-depleted liquid smoke was
evaluated using Calgon activated carbon TOG.
The batch procedure of Example 2 was repeated and
different gram levels of carbon (reported as g of C) were
mixed with 100 ml aliquots of liquid smoke (11% titratable
acidity) for 3 hours, followed by filtration to remove the
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carbon particles. Each of the resultant carbon-treated
liquid smoke samples was mixed with 2 times its volume of
water to judge miscibility. All water-diluted samples
were tar-containing as tar precipitate always formed
within 2 hours and the samples were cloudy.
It was found that although at a level of > 2.5 g of
the activated carbon, the carbon reduced the phenols
content of each carbon-treated liquid smoke sample, the
active sites were insufficient for removing tar-forming
materials from the phenols. Further in connection with
the phenols content of the carbon-treated liquid smoke
samples, it is noted that at a level from 0.05 g to 1.0 g
of carbon, the carbon reduced the phenols content of each
carbon-treated liquid smoke sample only by a de minimus
amount (i.e., < 1%) or actually increased the phenols
content or each carbon-treated liquid smoke sample.
Moreover, for those samples treated at a level of >
2.5 g of the activated carbon, wherein the carbon reduced
the phenols content, there is also a positive correlation
of the pH of the sample increasing, which, as can be seen
from reviewing Table 1, did not occur from treatment with
Calgon carbon APA.
The results are reported in the following Table 5
which shows the significant impact of lack of sufficient
activation sites on carbon ability for removal of the tar-
component of the phenols.
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TABLE 5
Sample Staining Carbonyls Phenols Water Tar
ci of C Acidity f %) pH Index fall 00 al m ml Dilution Settled
Code
10 feed
(none) 11.0 2.01 88.4 15.8 14.05 Cloudy Yes
0.05 11.2 2.02 85.3 14.5 16.13 Cloudy Yes
0.1 11.15 2.02 85.5 15.7 13.94 Cloudy Yes
0.2 11.0 2.04 84.0 14.4 16.20 Cloudy Yes
0.5 11.2 2.05 80.6 15.8 13.24 Cloudy Yes
1.0 11.0 2.07 80.0 15.1 16.51 Cloudy Yes
2.5 11.0 2.19 81.3 15.7 11.73 Cloudy Yes.
5.0 10.75 2.30 83.7 14.8 10.69 Cloudy Yes
10.0 10.8 2.47 83.7 13.9 9.23 Cloudy Yes
Example 6 (Treatment of Foodstuffs)-
Proteinaceous foodstuffs are treated with the tar-
depleted liquid smokes from Example 1 (samples 1 through
5), Example 2 (all samples of Table 2), Example 3 (all
samples of Table 3), and Example 4 (samples 3, 4 and 5),
and with these liquid smokes diluted with water up to 5x.
The foodstuffs thus treated by applying the tar-
depleted liquid smokes to the surface thereof are
sausages, frankfurters, beef rolls, hams, and bolognas.
Excellent staining and flavor is obtained.
Example 7 (Treatment of Food Casings)
Food casings are treated with the tar-depleted liquid
smokes from Example 1 (samples 1 through 5), Example 2
(all samples of Table 2), Example 3 (all samples of Table
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3) , and Example 4 (samples 3, 4, and 5) , and with these
liquid smokes diluted with water up to 5x.
Selected casings are cellulosic fibrous casings and
are treated by spraying the tar-depleted liquid smokes
onto the surface thereof.
Selected casings are extruded polymeric plastic films
and are treated by spraying the tar-depleted liquid smokes
onto the surface thereof.
Selected casings are extruded polymeric plastic films
and are treated by incorporating the tar-depleted liquid
smokes into the extruder with the polymeric resin beads
and thus blending-the smokes into the resultant films.
The polymeric plastic films are of ethylene vinyl
acetate, ethylene acrylic acid, ethylene methacrylic acid,
linear low density polyethylene, and very low density
linear low density polyethylene.
The foodstuffs of Example 6 are packaged with the
various casings, and the packaged foodstuffs have
excellent staining and flavor.
It will be understood that various details of the
invention may be changed without departing from the scope
of the invention. Furthermore, the foregoing description
is for the purpose of illustration only, and not for the
purpose of limitation--the invention being defined by the
claims.
